JP7103642B2 - Deodorant and deodorant sheet - Google Patents

Description

The present invention relates to a deodorizing material and a deodorizing sheet.

In recent years, there has been increasing interest in air purification, and there is a demand for an environment with less foul odor, such as indoors. In addition, with the problem of sick house syndrome as a starting point, countermeasures against volatile organic compounds (VOCs) in the living environment are also required.

For example, in the passenger compartment of an automobile, the odor of volatile organic compounds from interior resin parts such as seat pads, instrument panels, door trims, paints, adhesives, etc., as well as exhaust gas, fuel odor, tobacco, and the human body Many foul odors can occur, such as food spoilage. Further, since the space inside the vehicle interior is smaller than that of a house, there is a problem that a bad odor is particularly likely to be filled when the vehicle interior is sealed.

Patent Document 1 discloses a fibrous deodorant containing fibrous activated carbon, aromatic amino acids and sulfuric acid, which is produced by a method including the following steps.
It is a step of immersing a fibrous activated charcoal in an aqueous solution containing an aromatic amino acid and sulfuric acid to support the aromatic amino acid and sulfuric acid on the fibrous activated charcoal, and the mass ratio of the aromatic amino acid to the fibrous activated charcoal is 10 mass by mass. The step of setting the mass ratio of sulfuric acid to the fibrous activated carbon in the range of 5% by mass to 25% by mass, and the step of setting it in the range of% to 20% by mass.
The step of removing the aqueous solution from the fibrous activated carbon supporting aromatic amino acids and sulfuric acid, and
The process of drying the fibrous activated carbon from which the aqueous solution has been removed.

Japanese Unexamined Patent Publication No. 2011-72003

The present inventor wants to more efficiently exhibit the adsorption performance of acetaldehyde by carrying aromatic amino acids and sulfuric acid on activated carbon in the deodorizing material disclosed in Patent Document 1. That is, it was considered that the acetaldehyde adsorption performance could be further improved when the same amount of aromatic amino acids and sulfuric acid were supported on the activated carbon.

Therefore, the present invention solves the above-mentioned problems, and when a deodorizing material is prepared by supporting aromatic amino acids and sulfuric acid on activated carbon under the same immersion conditions, the deodorizing material efficiently exhibits the acetaldehyde adsorption performance of the deodorizing material. The main purpose is to provide.

The present inventor has made diligent studies to solve such a problem. As a result, when the aromatic amino acid and the sulfuric acid were supported on activated carbon having a pore diameter of 0.65 nm or more and 2.0 nm or less and a pore volume of 0.6 cc / g or more, the aromatic amino acid and sulfuric acid were subjected to the same immersion conditions. Excellent acetaldehyde adsorption as compared with the case where sulfuric acid is supported on an activated carbon other than the above activated carbon, that is, an activated carbon having a pore diameter of 0.65 nm or more and 2.0 nm or less and a pore volume of less than 0.6 cc / g. We have found that it demonstrates its performance. The present invention is an invention completed by further studying based on these findings.

That is, the present invention provides the inventions of the following aspects.
Item 1. A deodorant containing the activated charcoal and (A) aromatic amine and sulfate of the aromatic amine supported on the activated charcoal, or (B) aromatic amine, sulfate of the aromatic amine, and sulfuric acid. And
The activated carbon is a deodorizing material having a pore diameter of 0.65 nm or more and 2.0 nm or less and a pore volume of 0.6 cc / g or more.
Item 2. Item 1. The deodorizing material according to Item 1, wherein the activated carbon has a total pore volume (cc / g) that is 1 to 2 times the pore volume having a pore diameter of 0.65 nm or more and 2.0 nm or less.
Item 3. Item 2. The deodorizing material according to Item 1 or 2, wherein the pore volume of the activated carbon having a pore diameter of 3 nm or more is 0.02 cc / g or less.
Item 4. Item 2. The deodorant according to any one of Items 1 to 3, wherein the activated carbon has a specific surface area of 1500 m ² / g or more.
Item 5. Item 2. The deodorizing material according to any one of Items 1 to 4, wherein the specific surface area of the deodorizing material is 400 to 1200 m ² / g.
Item 6. Item 2. The deodorizing material according to any one of Items 1 to 5, wherein the value obtained by subtracting the specific surface area of the deodorizing material from the specific surface area of the activated carbon is 800 to 1300 m ² / g.
Item 7. Item 2. The deodorant according to any one of Items 1 to 6, wherein the equilibrium adsorption amount (mg / gACF) of acetaldehyde at an equilibrium concentration of 10 ppm is 35 mg / gACF or more.
Item 8. A deodorizing sheet containing the deodorizing material according to any one of Items 1 to 7.

The deodorizing material of the present invention comprises activated carbon and (A) aromatic amine and sulfate of the aromatic amine supported on the activated carbon, or (B) aromatic amine, sulfate of the aromatic amine, and It is a deodorizing material containing sulfuric acid, and since the activated carbon has a pore volume of 0.65 nm or more and 2.0 nm or less and a pore volume of 0.6 cc / g or more, excellent acetaldehyde adsorption performance is efficiently achieved. Can be demonstrated. Further, the deodorizing sheet containing the deodorizing material of the present invention can also efficiently exhibit excellent acetaldehyde adsorption performance.

The deodorizing material of the present invention comprises activated carbon and (A) aromatic amine and sulfate of the aromatic amine supported on the activated carbon, or (B) aromatic amine, sulfate of the aromatic amine, and A deodorizing material containing sulfate, the activated carbon is characterized by having a pore volume of 0.65 nm or more and 2.0 nm or less and a pore volume of 0.6 cc / g or more. Hereinafter, the deodorizing material of the present invention and the deodorizing sheet using the deodorizing material will be described in detail.

In the following, the pore volume refers to the pore volume calculated by the QSDFT method (quenched solid density functional theory). The QSDFT method is an analysis method that can calculate the pore size distribution from about 0.5 nm to about 40 nm for the pore size analysis of geometrically and chemically irregular microporous and mesoporous carbon. .. In the QSDFT method, the influence of the roughness and non-uniformity of the pore surface is clearly taken into consideration, so that the accuracy of the pore diameter distribution analysis is greatly improved. In the present invention, the nitrogen adsorption isotherm is measured using "AUTOSORB-1-MP" manufactured by Quantachrome, and the pore size distribution is analyzed by the QSDFT method. By applying N2 at 77K on carbon [slit pore, QSDFT equilibrium model] as the Calcation model to the nitrogen desorption isotherm measured at a temperature of 77K, the pore size distribution is calculated to reduce the specific pore size range. The hole volume can be calculated.

The deodorizing material of the present invention comprises activated charcoal and (A) "aromatic amine and sulfate of the aromatic amine" or (B) "aromatic amine, sulfate of the aromatic amine, and sulfate". include. When the deodorizing material of the present invention contains an activated charcoal, an aromatic amine and a sulfate of the aromatic amine, (A) the aromatic amine and the sulfate of the aromatic amine are supported on the activated charcoal. ing. Further, when the deodorizing material of the present invention contains activated charcoal, (B) aromatic amine, a sulfate of the aromatic amine, and sulfuric acid, the aromatic amine, the sulfate of the aromatic amine, and Sulfate is carried on the activated carbon.

In the deodorizing material of the present invention, (A) aromatic amine and sulfate of the aromatic amine, or (B) aromatic amine, sulfate of the aromatic amine, and sulfate (hereinafter collectively referred to as "the present invention". The activated carbon carrying the "drug contained in the deodorizing material") has a pore volume of 0.65 nm or more and 2.0 nm or less and a pore volume of 0.6 cc / g or more. By using activated carbon having such a specific pore distribution, excellent acetaldehyde adsorption performance can be efficiently exhibited.

In the deodorizing material of the present invention, the following can be considered as the reason why the excellent acetaldehyde adsorption performance is efficiently exhibited by using the activated carbon having the above-mentioned specific pore distribution. That is, since acetaldehyde has a small molecular size, it was considered that small pores of activated carbon adsorbing acetaldehyde are preferable. However, according to the study by the present inventor, it has been clarified that the chemical contained in the deodorizing material of the present invention is likely to be supported on the pore diameter in the range of 0.65 to 2.0 nm of the activated carbon. More specifically, when the distribution of activated carbon pores before and after carrying the drug was examined, the reduction rate of the pore volume in the range of 0.65 to 2.0 nm was high. This is considered to indicate that more of the above-mentioned drug is supported in the pores having a pore diameter in the range, among all the pore diameters. Therefore, by using activated carbon having the specific pore distribution, the drug can be easily supported in the pores, and the adsorption effect by the pores and the contact between the drug and acetaldehyde due to the support in the pores of the drug. It is considered that the synergistic effect of the area improvement effect is likely to occur, and as a result, excellent acetaldehyde adsorption performance can be efficiently exhibited.

The pore volume having a pore diameter of 0.65 nm or more and 2.0 nm or less is preferably 0.7 cc / g or more, and more preferably 0.75 cc / g or more, from the viewpoint of more efficiently exhibiting acetaldehyde adsorption performance. The upper limit of the pore volume is not particularly limited, and examples thereof include 1.2 cc / g or less and 1.0 cc / g or less. In addition, in this specification, the description of activated carbon is the one before carrying the agent contained in the deodorant of the present invention, unless otherwise explained.

In the deodorizing material of the present invention, the total pore volume of the activated carbon is 0.65 nm or more from the viewpoint of further improving the adsorption performance of acetaldehyde while ensuring the pore volume of the pore diameter of 0.65 nm or more and 2.0 nm or less. The pore volume having a pore diameter of 2.0 nm or less is about 1 to 2 times, preferably about 1.1 to 1.4 times. Specifically, for example, 0.7 to 2.0 cc / g is mentioned, and 0.7 to 1.2 cc / g is preferably mentioned.

In the deodorizing material of the present invention, the ratio of the pore volume of the activated carbon to the pore volume of 0.65 nm or more and 2.0 nm or less (the pore volume of the pore diameter of 0.65 nm or more and 2.0 nm or less / total). The pore volume) is, for example, 0.6 to 0.9, preferably 0.7 to 0.85, and more preferably 0.7 to 0.75.

In the deodorizing material of the present invention, the pore volume of the activated carbon having a pore diameter of 2 nm or less is 0.65 nm or more and 2.0 nm or less, and the adsorption performance of acetaldehyde is further improved. From the viewpoint, for example, 0.7 to 0.9 cc / g is preferably mentioned, and 0.85 to 0.9 cc / g is more preferably mentioned. Further, the ratio of the pore volume having a pore diameter of 2 nm or less to the total pore volume (pore volume having a pore diameter of 2 nm or less / total pore volume) is 0.8 to 0.98 from the same viewpoint. It is preferably mentioned, and more preferably 0.80 to 0.85.

In the deodorizing material of the present invention, as the pore volume of the activated carbon having a pore diameter of 0.65 nm or less, the adsorption performance of acetaldehyde is further improved while ensuring the pore volume of the pore diameter of 0.65 nm or more and 2.0 nm or less. From the viewpoint of improvement, for example, 0.05 to 0.12 cc / g is preferably mentioned, and 0.08 to 0.1 cc / g is more preferably mentioned. Further, the ratio of the pore volume having a pore diameter of 0.65 nm or less to the total pore volume (pore volume having a pore diameter of 0.65 nm or less / total pore volume) is 0.05 to 0.05 to that of the same viewpoint. 0.20 is preferable, and 0.05 to 0.12 is more preferable.

In the deodorizing material of the present invention, as the pore volume of the activated carbon having a pore diameter of 2 nm or more and 3 nm or less, the adsorption performance of acetaldehyde is further improved while ensuring the pore volume of the pore diameter of 0.65 nm or more and 2.0 nm or less. From the viewpoint of improvement, 0.01 to 0.2 cc / g is preferably mentioned, and 0.15 to 0.2 cc / g is more preferably mentioned. The ratio of the pore volume having a pore diameter of 2 nm or more and 3 nm or less to the total pore volume (pore volume having a pore diameter of 2 nm or more and 3 nm or less / total pore volume) is 0.01 to 0.01 to the total pore volume. 0.20 is preferably mentioned, and 0.15 to 0.20 is more preferably mentioned.

In the deodorizing material of the present invention, the pore volume of the activated carbon having a pore diameter of 3 nm or more is larger than that of the pore diameter in the range while ensuring a pore volume of 0.65 nm or more and 2.0 nm or less. From the viewpoint of facilitating the carrying of the drug contained in the deodorant of the present invention, 0.02 cc / g or less is preferably mentioned, and 0.01 cc / g or less is more preferably mentioned.

In the deodorizing material of the present invention, the specific surface area of the activated carbon is 1500 m ² / from the viewpoint of ensuring the pore volume with a pore diameter of 0.65 nm or more and 2.0 nm or less and improving the acetaldehyde adsorption performance. It is preferably g or more, and more preferably 1900 m ² / g or more. The upper limit is not particularly limited, and examples thereof include 3500 m ² / g or less and 2500 m ² / g or less. The specific surface area of activated carbon is a value obtained by the BET method (one-point method) described in JIS K1477.

In the deodorizing material of the present invention, the form of activated carbon is not particularly limited, and examples thereof include granular activated carbon, powdered activated carbon, and fibrous activated carbon. From the viewpoint that the adsorption rate of acetaldehyde is relatively high, it is more preferable to use fibrous activated carbon which is fibrous. The average fiber diameter of the fibrous activated carbon is preferably 30 μm or less, more preferably about 5 to 20 μm. The average fiber diameter in the present invention is an image processing fiber diameter measuring device (JIS).
It is a value measured by K 1477). Further, as the particle size of the granular activated carbon and the powdered activated carbon, the integrated volume percentage D50 measured by the laser diffraction / scattering method is 0.01 to 5 mm.

The raw material type and form of the activated carbon precursor are not particularly limited. Examples of the raw material species of the activated carbon precursor include infusible or carbonized organic materials, curable resins such as phenol resins, and the like, and examples of the organic materials include polyacrylonitrile, pitch, polyvinyl alcohol, cellulose and the like. Can be mentioned. Also, oga scraps, wood chips, wood, peat, charcoal, coconut shells, coal, oil, carbonaceous substances (petroleum coke, coal coke, oil pitch, coal pitch, coal tar pitch, and composites thereof, etc.), synthetic Examples thereof include resins (phenolic resin, polyacrylonitrile (PAN), polyimide, furan resin, etc.), cellulose-based fibers (paper, cotton fiber, etc.), composites thereof (paper-phenol resin laminated board, etc.), fullerene, and the like. Among these, in terms of the theoretical carbonization yield at the time of carbonization, the pitch is preferable, and the coal pitch is more preferable. Examples of the form of the activated carbon precursor include granular, powdery, fibrous and the like.

The method for obtaining the activated carbon used for the deodorizing material of the present invention is not particularly limited, but for example, the activation temperature and activation time of the activated carbon precursor are adjusted by using steam so as to have a predetermined pore distribution. There is a way to get it.

In the deodorizing material of the present invention, the aromatic amine is not particularly limited, but halogen and sulfo are used to more effectively enhance the deodorizing ability for toluene and ammonia in addition to acetaldehyde, and from the viewpoint of ease of handling and safety in production. Aromatic amines in which a group, an acetamido group, or a carbonyl group is bonded to a benzene ring are preferable. Preferred examples of the aromatic amine having a halogen, a sulfo group, an acetamido group, or a carbonyl group bonded to a benzene ring include aminobenzoic acid, aminoacetanilide, aminosalicylic acid, and aminosulfanilic acid. Among them, aminobenzoic acid and its sulfate are preferable as the aromatic amine and the sulfate of the aromatic amine. That is, in the deodorizing material of the present invention, it is preferable that aminobenzoic acid and a sulfate thereof are supported on the fibrous activated carbon. In the deodorizing material of the present invention, at least a part of the aromatic amine forms a sulfate together with sulfuric acid described later. The aromatic amine and the sulfate of the aromatic amine may be used alone or in combination of two or more.

The aminobenzoic acid is not particularly limited, and at least one of p-aminobenzoic acid, m-aminobenzoic acid, and o-aminobenzoic acid can be used. From the viewpoint of more effectively enhancing the deodorizing ability for toluene and ammonia in addition to acetaldehyde, it is particularly preferable that p-aminobenzoic acid is supported in the deodorizing material of the present invention.

In the deodorizing material of the present invention, sulfuric acid may be carried together with the above aromatic amine and the sulfate of the aromatic amine. That is, the deodorizing material of the present invention comprises (A) an active carbon carrying an aromatic amine and a sulfate of the aromatic amine (sulfate may not be carried), or (B) an aromatic amine and the same. It is equipped with an activated carbon carrying an aromatic amine sulfate and sulfuric acid.

Sulfuric acid has a relatively high boiling point and is difficult to volatilize. Sulfuric acid promotes the dissolution of aminobenzoic acid in water, so that it is possible to uniformly support an aromatic amine and a sulfate of the aromatic amine in the activated carbon in the process of producing a deodorizing material as described later. .. Further, sulfuric acid exerts an effect of suppressing the polymerization of aromatic amines and sulfate salts of aromatic amines with each other in the deodorizing material.

In the deodorizing material of the present invention, the total carrying amount of the aromatic amine and the sulfate of the aromatic amine is not particularly limited, and for example, it may be 10 to 40 parts by mass with respect to 100 parts by mass of the activated carbon. From the viewpoint of further enhancing the acetaldehyde adsorption performance, 20 to 40 parts by mass is preferably mentioned, and 25 to 35 parts by mass is more preferably mentioned. Further, in the deodorizing material of the present invention, the total carrying amount of the sulfate and sulfuric acid of the aromatic amine is not particularly limited, and for example, it may be 0.5 to 5 parts by mass with respect to 100 parts by mass of the activated carbon. It is preferably 2 to 5 parts by mass.

The specific surface area of the deodorizing material of the present invention (specific surface area after carrying the drug contained in the deodorizing material of the present invention) is not particularly limited, and examples thereof include 400 to 1200 m ² / g and 500 to 1
100 m ² / g is preferably mentioned, and 700 to 1100 m ² / g is more preferably mentioned. The specific surface area can be, for example, 900 to 1200 m ² / g or 500 to 800 m ² / g.

In the deodorizing material of the present invention, the specific surface area (= specific surface area of activated carbon before loading-specific surface area of deodorizing material after loading) reduced by supporting the chemical contained in the deodorizing material of the present invention is, for example, 800 to 1300 m. ² / g is mentioned, and 900 to 1200 m ² / g is mentioned. Further, in the deodorizing material of the present invention, the reduction rate of the specific surface area of the activated carbon due to the support of the chemical contained in the deodorant of the present invention (= specific surface area of the deodorizing material after support / specific surface area of activated carbon before support × 100 ( %)) For example, 30 to 60% can be mentioned.

In the deodorizing material of the present invention, the equilibrium adsorption amount (mg / gACF) of acetaldehyde at an equilibrium concentration of 10 ppm is preferably 35 mg / gACF or more, more preferably 45 to 70 mg / gACF, and particularly preferably 50 to 60 mg / gACF. Be done. The methods for measuring the equilibrium adsorption amount of acetaldehyde at an equilibrium concentration of 10 ppm of the deodorant of the present invention are as follows.

(Measurement of equilibrium adsorption amount of acetaldehyde)
A sample piece of arbitrary weight and 3 L of 100 ppm acetaldehyde gas are sealed in a closed container and allowed to stand in an environment of 25 ° C. After 24 hours, the gas concentration in the container is measured and the adsorption amount is calculated. Measurements were made for multiple sample weights, the correlation between the concentration and the adsorption amount was plotted on a graph from each calculation result, and the equilibrium adsorption amount (mg / g ACF) of acetaldehyde at an arbitrary equilibrium concentration was calculated from the obtained relational expression. Guide. Gas chromatography or a gas detector tube is used to measure the concentration of acetaldehyde.

The deodorizing material of the present invention can be produced, for example, as follows. First, an activated carbon having a pore diameter of 0.65 nm or more and 2.0 nm or less and a pore volume of 0.6 cc / g or more is prepared. The method for obtaining the activated carbon is as described above. Next, a treatment liquid containing aromatic amine and / or a salt thereof, sulfuric acid and / or a salt thereof, and water is prepared. Aromatic amines and / or salts thereof may be dissolved in aqueous solutions of sulfuric acid and / or salts well diluted with water, or in aqueous solutions containing sulfuric acid and / or salts thereof in relatively high concentrations. After this, it may be diluted with water to prepare a treatment liquid. As the sulfuric acid, concentrated sulfuric acid or dilute sulfuric acid may be used. Further, in order to dissolve the aromatic amine and / or its salt in water, an aqueous solution of sulfuric acid and / or its salt is heated to a temperature in the range of, for example, 50 to 80 ° C., and the aromatic amine and / or its salt is here. The salt may be mixed. Further, as the aromatic amine, the above-mentioned one is used. The salt of the aromatic amine is not particularly limited, and examples thereof include a sulfate of the aromatic amine.

The amount of the aromatic amine and / or its salt charged in the treatment liquid is not particularly limited as long as the amount of the aromatic amine and / or its salt carried in the deodorizing material of the present invention is set within a desired range. For example, the amount may be about 12 to 40 parts by mass with respect to 100 parts by mass of the activated carbon to be immersed later. The amount of sulfuric acid and / or a salt thereof charged in the treatment liquid is the sulfate of the aromatic amine and the aromatic amine in the deodorizing material of the present invention, or the sulfate and sulfuric acid of the aromatic amine and the aromatic amine. The content of the above is not particularly limited as long as it is set to be in a desired range, and may be about 12 to 40 parts by mass with respect to 100 parts by mass of the activated carbon to be immersed later.

Next, the prepared activated charcoal is immersed in this treatment liquid to support the aromatic amine and the sulfate of the aromatic amine, or the aromatic amine and the sulfate and sulfuric acid of the aromatic amine. For example, the activated carbon is uniformly dispersed in the treatment liquid, and then the dispersion liquid is allowed to stand for a sufficient time. The time for immersing the activated carbon in the treatment liquid is, for example, about 1 hour or more. The ratio of the mass of the activated carbon to the volume of the treatment liquid is, for example, in the range of 5 to 50 g / L. If this ratio is too small, it takes a longer time to support the aromatic amine and the sulfate of the aromatic amine, or the aromatic amine and the sulfate and sulfuric acid of the aromatic amine on the activated charcoal. On the other hand, if this ratio is too large, it becomes difficult to uniformly support the aromatic amine and the sulfate of the aromatic amine, or the aromatic amine and the sulfate and sulfuric acid of the aromatic amine on the activated carbon. If the time during which the activated carbon is in contact with the aqueous solution is sufficiently long, this ratio is the sulfate of the aromatic amine and the aromatic amine supported on the activated carbon, or the sulfate of the aromatic amine and the aromatic amine. And the effect on the amount of sulfate can be ignored. The treatment liquid for immersing the activated carbon may be used in a heated state at the time of charging the above aromatic amine and / or a salt thereof, or may be used after cooling the heated treatment liquid.

Next, the treatment liquid is removed from the activated carbon carrying the aromatic amine and the sulfate of the aromatic amine, or the aromatic amine and the sulfate and sulfuric acid of the aromatic amine. The method for removing the treatment liquid is not particularly limited, and for example, it can be carried out by pulling activated carbon from the treatment liquid. The treatment liquid is diluted with water prior to removal of the treatment liquid from the active carbon carrying the aromatic amine and the sulfate of the aromatic amine or the sulfate and sulfuric acid of the aromatic amine and the aromatic amine. May be.

Then, the activated carbon from which the treatment liquid has been removed is dried. For this drying, for example, natural drying, ventilation drying, hot air drying, microwave heating drying, indirect heating drying and the like can be used. Drying is carried out so that the temperature of the activated carbon is maintained at, for example, 130 ° C. or lower, preferably 80 ° C. or lower. As described above, the deodorizing material of the present invention can be produced.

Next, the deodorizing sheet of the present invention will be described in detail. The deodorizing sheet of the present invention uses the above-mentioned deodorizing material of the present invention, and includes the deodorizing material of the present invention. Specifically, the deodorizing sheet of the present invention is, for example, a sheet formed by the above-mentioned deodorizing material. The form of the sheet is not particularly limited, but a non-woven fabric is preferable. The deodorizing sheet of the present invention may contain a binder, if necessary, for the purpose of molding the above-mentioned deodorizing material into a sheet shape. The binder is not particularly limited as long as it can bond the activated carbons constituting the deodorizing material to each other. Can be used.

When the deodorizing sheet of the present invention contains a binder, the mass ratio (binder / deodorizing material) between the binder and the deodorizing material of the present invention is preferably about 75/25 to 25/75. Further, when the density of the deodorizing sheet is lowered, which will be described later, the deodorizing ability with respect to acetaldehyde is further improved, so that the mass ratio of activated carbon can be easily reduced. For example, the binder and the present invention. The mass ratio (binder / deodorant material) of the above to the deodorizing material is easily set to about 75/25 to 65/35.

The density of the deodorizing sheet of the present invention is not particularly limited, but from the viewpoint of further improving the deodorizing ability against acetaldehyde, for example, 0.05 to 0.3 g / cm ³ is preferable, and 0. 05 to 0.20 g / cm ³ is more preferable, and 0.08 to 0.15 g / cm ³ is particularly preferable. Further, when the thickness of the deodorizing sheet of the present invention is, for example, 0.15 to 0.80 mm, preferably 0.3 to 0.7 mm, the deodorizing ability is excellent and the inside of the seat cover in the vehicle interior is covered. It will be easier to accommodate. As a method for obtaining a sheet having a low density and / or a thin sheet as described above, for example, a thin non-woven fabric having a basis weight of about 1 to 8 g / m ² is produced, and a plurality of layers of the non-woven fabric are laminated and needle punched to be integrated. It can be obtained by making it.

The deodorizing sheet of the present invention can be produced, for example, by molding the above-mentioned deodorizing material into a sheet, or a fibrous activated carbon containing an aromatic amine and a sulfate of the aromatic amine, or an aromatic amine. After forming the sulphate of the aromatic amine and the fibrous activated charcoal before supporting the sulfuric acid into a sheet, the sheet is immersed in the treatment liquid in the same manner as described above, and the fragrant amine and the fragrance are added to the fibrous activated charcoal. It can also be produced by carrying a sulfate of a group amine or a sulfate of an aromatic amine and a sulfate and a sulfuric acid of the aromatic amine.

When the deodorizing sheet of the present invention is used as an air purification sheet, a dust removing sheet such as an electretized non-woven fabric sheet, a HEPA (high effective particulate air) filter, or a ULPA (ultra low penetration air) filter is attached to the deodorizing sheet. It is also possible to obtain a laminated body having a dust removing effect. Such a laminate can be suitably used in an air purifier or the like that performs air purification and dust removal.

Since the deodorizing sheet of the present invention contains the deodorizing material of the present invention described above, acetaldehyde can be removed from the gas phase with high efficiency. Therefore, the deodorizing sheet of the present invention can be widely used in a living environment, and can be suitably used for interior materials of automobiles, trains, ships, airplanes, and the like. Above all, the deodorizing sheet of the present invention can be used by accommodating acetaldehyde in the cover of the seat in the vehicle interior as an automobile interior material capable of removing acetaldehyde from the gas phase with high efficiency. That is, it can be an interior seat including the deodorizing seat of the present invention. Further, the deodorizing material of the present invention has a deodorizing ability not only for acetaldehyde but also for lower aldehydes such as formaldehyde.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

[Test Example A]
<Example 1A>
Preparation of activated carbon
The granular coal pitch was supplied to a melt extruder, melt-mixed at a melting temperature of 320 ° C., and spun at a discharge rate of 20 g / min to obtain pitch fibers. The obtained pitch fibers were subjected to infusibilization treatment by raising the temperature in air from room temperature to 354 ° C. at a rate of 1 to 30 ° C./min for 54 minutes to obtain an activated carbon precursor which is an infusible pitch fiber. The obtained activated carbon precursor was activated by continuously introducing a gas having an _H2O concentration of 100% by volume into an activation furnace and heat-treating at an atmospheric temperature of 875 ° C. for 70 minutes to obtain a fibrous activated carbon. .. The pore volume of the obtained fibrous activated carbon having a pore diameter of 0.65 nm or more and 2.0 nm or less was 0.781 cc / g. The total pore volume is 1.058 cc / g, the pore volume with a pore diameter of 2 nm or less is 0.877 cc / g, the specific surface area is 2069 m ² / g, and the pore volume with a pore diameter of 0.65 nm or less is 0. The pore volume of 0.096 cc / g and the pore diameter of 2 nm or more and 3 nm or less was 0.174 cc / g, and the pore volume of the pore diameter of 3 nm or more was 0.007 cc / g. In the examples, the pore volume having a pore diameter of 2 nm or more and 3 nm or less is determined by determining the pore volume having a pore diameter of 3 nm or less, and the pore volume having a pore diameter of 2 nm or less is reduced from the pore volume. Obtained by. The pore volume having a pore diameter of 3 nm or more was determined by subtracting the pore volume having a pore diameter of 3 nm or less from the total pore volume.

Preparation of Chemical Solution A Contained in Deodorant of the Present Invention First, a sulfuric acid aqueous solution containing sulfuric acid at a concentration of 75% by mass was prepared. This sulfuric acid aqueous solution is stirred at a temperature of 65 ° C. or higher, p-aminobenzoic acid as an aromatic amine is added to the aqueous solution to completely dissolve it, and then the ratio of the mass of the activated charcoal to the volume of the treatment liquid is 20 g / L. Water was added so as to obtain a treatment liquid. The amount of aromatic amine and sulfuric acid charged was 15.0 parts by mass with respect to 100 parts by mass of activated carbon. The amount of sulfuric acid charged (parts by mass) indicates the amount (parts by mass) of sulfuric acid only excluding pure water in a 75 mass% sulfuric acid aqueous solution.

Supporting the chemical contained in the deodorant of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the chemical solution A. Subsequently, the solution was stirred for 10 minutes to evenly disperse the activated carbon in the solution. Then, this dispersion was allowed to stand. After allowing to stand for 8 hours or more, the activated carbon was withdrawn from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain the deodorizing material of Example 1A. In the deodorizing material, the total carrying amount (parts by mass) of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the activated charcoal, and the total carrying amount of the sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( (Mass part) was measured as follows.

Measurement of the total carrying amount (parts by mass) of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the activated charcoal The organic matter concentration of the solution before dipping the active charcoal and the liquid after soaking the activated charcoal were measured using a total organic matter concentration (TOC) meter, and the total carrying amount was determined from the difference in the organic matter concentration before and after the dipping operation. Was measured. Specifically, first, using a total organic matter concentration (TOC) meter (TOC-5000 manufactured by Shimadzu Corporation), the organic matter concentration (mgC / L) converted into carbon (C) was obtained for the chemical solution before and after the immersion operation. Was measured, and the difference in concentration before and after the operation was determined. Separately, the total organic substance concentration is measured in the same manner for the aromatic amine aqueous solution having a known concentration prepared by weighing, and a calibration line showing the correspondence between the organic substance concentration (mgC / L) and the aromatic amine concentration (mg aromatic amine / L). It was created. Using the prepared calibration curve, the difference in organic matter concentration (mgC / L) before and after the attachment operation was converted into the difference in aromatic amine concentration (mg aromatic amine / L). The difference in aromatic amine mass was calculated by multiplying the obtained difference in concentration by the amount of treatment liquid (L). The calculated value was converted into parts by mass per 100 parts by mass of the active charcoal before being immersed in the chemical solution, and the obtained parts by mass was the sum of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the active charcoal. The amount carried (parts by mass) was used.

Measurement of the total amount of aromatic amine sulfate and sulfuric acid carried (parts by mass) with respect to 100 parts by mass of activated charcoal Similarly, the total amount of substance of aromatic amine sulfate and sulfuric acid carried on the activated charcoal is also before the activated charcoal is immersed. By measuring the concentration of sulfate ion (mg / L) according to the ion chromatograph method specified in JIS K 0101: 1998 42.4, the total of the drug solution and the drug solution after immersion in the activated charcoal. The carrying amount was calculated. Specifically, the sulfate ion concentration (mg / L) of the drug solution before and after the immersion operation was measured using a calibration curve, respectively, and the difference in sulfate ion concentration (mg / L) before and after the operation was determined. Multiply the difference in sulfate ion concentration (mg / L) before and after the calculated operation by the ratio of the molecular weight of sulfuric acid (98.08 g / mol) and the molecular weight of sulfate ion (96.06 g / mol) to convert to the difference in sulfate concentration. did. The difference in sulfuric acid before and after the operation was calculated by multiplying the difference in sulfuric acid concentration by the amount of the treatment liquid (L). The calculated difference in sulfuric acid before and after the operation was converted into parts by mass per 100 parts by mass of activated charcoal before immersion in the chemical solution, and the obtained parts by mass was converted into parts of aromatic amine sulfate and sulfuric acid with respect to 100 parts by mass of activated charcoal. The total amount carried (parts by mass) was used.

<Comparative Example 1A>
Preparation of activated carbon
The granular coal pitch was supplied to a melt extruder, melt-mixed at a melting temperature of 320 ° C., and spun at a discharge rate of 20 g / min to obtain pitch fibers. The obtained pitch fibers were subjected to infusibilization treatment by raising the temperature in air from room temperature to 354 ° C. at a rate of 1 to 30 ° C./min for 54 minutes to obtain an activated carbon precursor which is an infusible pitch fiber. The obtained activated carbon precursor was activated by continuously introducing a gas having an _H2O concentration of 100% by volume into an activation furnace and heat-treating at an atmospheric temperature of 875 ° C. for 30 minutes to obtain a fibrous activated carbon. .. The pore volume of the obtained fibrous activated carbon having a pore diameter of 0.65 nm or more and 2.0 nm or less was 0.116 cc / g. The total pore volume is 0.315 cc / g, the pore volume with a pore diameter of 2 nm or less is 0.315 cc / g, the specific surface area is 825 m ² / g, and the pore volume with a pore diameter of 0.65 nm or less is 0. . 199 cc / g, the pore volume with a pore diameter of 2 nm or more and 3 nm or less was 0.000 cc / g, and the pore volume with a pore diameter of 3 nm or more was 0.000 cc / g.

Supporting the chemical contained in the deodorant of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the chemical solution A prepared in Example 1A. Subsequently, the solution was stirred for 10 minutes to evenly disperse the activated carbon in the solution. Then, this dispersion was allowed to stand. After allowing to stand for 8 hours or more, the activated carbon was withdrawn from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 1A. In the deodorizing material, the total carrying amount (parts by mass) of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the activated charcoal, and the total carrying amount of the sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( (Mass part) was measured in the same manner as in Example 1A.

<Comparative Example 2A>
Preparation of activated carbon
The granular coal pitch was supplied to a melt extruder, melt-mixed at a melting temperature of 320 ° C., and spun at a discharge rate of 20 g / min to obtain pitch fibers. The obtained pitch fibers were subjected to infusibilization treatment by raising the temperature in air from room temperature to 354 ° C. at a rate of 1 to 30 ° C./min for 54 minutes to obtain an activated carbon precursor which is an infusible pitch fiber. The obtained activated carbon precursor was activated by continuously introducing a gas having an _H2O concentration of 100% by volume into an activation furnace and heat-treating at an atmospheric temperature of 875 ° C. for 40 minutes to obtain a fibrous activated carbon. .. The pore volume of the obtained fibrous activated carbon having a pore diameter of 0.65 nm or more and 2.0 nm or less was 0.255 cc / g. The total pore volume is 0.476 cc / g, the pore volume with a pore diameter of 2 nm or less is 0.476 cc / g, the specific surface area is 1232 m ² / g, and the pore volume with a pore diameter of 0.65 nm or less is 0. .211 cc / g, the pore volume with a pore diameter of 2 nm or more and 3 nm or less was 0.000 cc / g, and the pore volume with a pore diameter of 3 nm or more was 0.000 cc / g.

Supporting the chemical contained in the deodorant of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the chemical solution A prepared in Example 1A. Subsequently, the solution was stirred for 10 minutes to evenly disperse the activated carbon in the solution. Then, this dispersion was allowed to stand. After allowing to stand for 8 hours or more, the activated carbon was withdrawn from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 2A. In the deodorizing material, the total carrying amount (parts by mass) of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the activated charcoal, and the total carrying amount of the sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( (Mass part) was measured in the same manner as in Example 1A.

<Comparative Example 3A>
Preparation of activated carbon
As an organic material, a mixture of 100 parts by mass of granular coal pitch having a softening point of 280 ° C. and 1.3 parts by mass of trisacetylacetonatoitorium was supplied to a melt extruder and melt-mixed at a melting temperature of 320 ° C. Pitch fibers were obtained by spinning at a discharge rate of 20 g / min. The obtained pitch fibers were subjected to infusibilization treatment by raising the temperature in air from room temperature to 354 ° C. at a rate of 1 to 30 ° C./min for 54 minutes to obtain an activated carbon precursor which is an infusible pitch fiber. The obtained activated carbon precursor was activated by continuously introducing a gas having an _H2O concentration of 100% by volume into an activation furnace and heat-treating at an atmospheric temperature of 900 ° C. for 20 minutes to obtain a fibrous activated carbon. .. The pore volume of the obtained fibrous activated carbon having a pore diameter of 0.65 nm or more and 2.0 nm or less was 0.335 cc / g. The total pore volume is 0.572 cc / g, the pore volume with a pore diameter of 2 nm or less is 0.395 cc / g, the specific surface area is 1078 m ² / g, and the pore volume with a pore diameter of 0.65 nm or less is 0. The pore volume with a pore diameter of 2 nm or more and 3 nm or less was 0.113 cc / g, and the pore volume with a pore diameter of 3 nm or more was 0.050 cc / g.

Supporting the chemical contained in the deodorant of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the chemical solution A prepared in Example 1A. Subsequently, the solution was stirred for 10 minutes to evenly disperse the activated carbon in the solution. Then, this dispersion was allowed to stand. After allowing to stand for 8 hours or more, the activated carbon was withdrawn from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 3A. In the deodorizing material, the total carrying amount (parts by mass) of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the activated charcoal, and the total carrying amount of the sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( (Mass part) was measured in the same manner as in Example 1A.

Using the deodorizing materials obtained in Example 1A and Comparative Examples 1A to 3A, the specific surface area and the amount of acetaldehyde equilibrium adsorption were measured according to the above-mentioned method. Further, the specific surface area of the activated carbon was subtracted from the specific surface area of the obtained deodorant, and the specific surface area reduced by the support of aromatic amine and sulfuric acid was calculated. Further, the acetaldehyde equilibrium adsorption amount was evaluated by the ratio when the equilibrium adsorption amount of Comparative Example 2A was 1. The results are shown in Table 1.

<Summary of Test Example A>
Example 1A includes activated carbon and (A) aromatic amine and sulfate of the aromatic amine, or (B) aromatic amine, sulfate of the aromatic amine, and sulfuric acid carried on the activated carbon. Since the activated carbon has a pore volume of 0.65 nm or more and 2.0 nm or less and a pore volume of 0.6 cc / g or more, it is a deodorizing material containing Compared to the case where the activated carbon other than the above activated carbon is supported, that is, the activated carbon of Comparative Examples 1A to 3A having a pore diameter of 0.65 nm or more and 2.0 nm or less and a pore volume of less than 0.6 cc / g. It exhibited excellent acetaldehyde adsorption performance.

[Test Example B]
<Example 1B>
Preparation of activated carbon
The activated carbon obtained in Example 1A was prepared.

Preparation of Chemical Solution B Contained in Deodorant of the Present Invention First, a sulfuric acid aqueous solution containing sulfuric acid at a concentration of 75% by mass was prepared. This sulfuric acid aqueous solution is stirred at a temperature of 65 ° C. or higher, p-aminobenzoic acid as an aromatic amine is added to the aqueous solution to completely dissolve it, and then the ratio of the mass of the activated charcoal to the volume of the treatment liquid is 20 g / L. Water was added so as to obtain a treatment liquid. The amount of aromatic amine and sulfuric acid charged was set to 22.5 parts by mass with respect to 100 parts by mass of activated carbon. The amount of sulfuric acid charged (parts by mass) indicates the amount (parts by mass) of sulfuric acid in the 75 aqueous sulfuric acid solution excluding pure water.

Supporting the chemical contained in the deodorant of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the chemical solution B. Subsequently, the solution was stirred for 10 minutes to evenly disperse the activated carbon in the solution. Then, this dispersion was allowed to stand. After allowing to stand for 8 hours or more, the activated carbon was pulled out of the solution and dried at 80 ° C. for 3 hours using a dryer to obtain the deodorizing material of Example 1B. In the deodorizing material, the total carrying amount (parts by mass) of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the activated charcoal, and the total carrying amount of the sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( (Mass part) was measured in the same manner as in Example 1A.

<Example 2B>
Preparation of activated carbon
The granular coal pitch was supplied to a melt extruder, melt-mixed at a melting temperature of 320 ° C., and spun at a discharge rate of 20 g / min to obtain pitch fibers. The obtained pitch fibers were subjected to infusibilization treatment by raising the temperature in air from room temperature to 354 ° C. at a rate of 1 to 30 ° C./min for 54 minutes to obtain an activated carbon precursor which is an infusible pitch fiber. The obtained activated carbon precursor was activated by continuously introducing a gas having an _H2O concentration of 100% by volume into an activation furnace and heat-treating at an atmospheric temperature of 875 ° C. for 50 minutes to obtain a fibrous activated carbon. .. The pore volume of the obtained fibrous activated carbon having a pore diameter of 0.65 nm or more and 2.0 nm or less was 0.622 cc / g. The total pore volume is 0.753 cc / g, the pore volume with a pore diameter of 2 nm or less is 0.728 cc / g, the specific surface area is 1731 m ² / g, and the pore volume with a pore diameter of 0.65 nm or less is 0. The pore volume of .106 cc / g and the pore diameter of 2 nm or more and 3 nm or less was 0.025 cc / g, and the pore volume of the pore diameter of 3 nm or more was 0.000 cc / g.

Supporting the chemical contained in the deodorant of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the chemical solution B prepared in Example 1B. Subsequently, the solution was stirred for 10 minutes to evenly disperse the activated carbon in the solution. Then, this dispersion was allowed to stand. After allowing to stand for 8 hours or more, the activated carbon was withdrawn from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain the deodorizing material of Example 2B. In the deodorizing material, the total carrying amount (parts by mass) of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the activated charcoal, and the total carrying amount of the sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( (Mass part) was measured in the same manner as in Example 1A.

<Comparative Example 1B>
Preparation of activated carbon
The activated carbon obtained in Comparative Example 1A was prepared.

Supporting the chemical contained in the deodorant of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the chemical solution B prepared in Example 1B. Subsequently, the solution was stirred for 10 minutes to evenly disperse the activated carbon in the solution. Then, this dispersion was allowed to stand. After allowing to stand for 8 hours or more, the activated carbon was withdrawn from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 1B. In the deodorizing material, the total carrying amount (parts by mass) of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the activated charcoal, and the total carrying amount of the sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( (Mass part) was measured in the same manner as in Example 1A.

<Comparative Example 2B>
Preparation of activated carbon
The activated carbon obtained in Comparative Example 2A was prepared.

Supporting the chemical contained in the deodorant of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the chemical solution B prepared in Example 1B. Subsequently, the solution was stirred for 10 minutes to evenly disperse the activated carbon in the solution. Then, this dispersion was allowed to stand. After allowing to stand for 8 hours or more, the activated carbon was withdrawn from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 2B. In the deodorizing material, the total carrying amount (parts by mass) of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the activated charcoal, and the total carrying amount of the sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( (Mass part) was measured in the same manner as in Example 1A.

<Comparative Example 3B>
Preparation of activated carbon
The activated carbon obtained in Comparative Example 3A was prepared.

Supporting the chemical contained in the deodorant of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the chemical solution B prepared in Example 1B. Subsequently, the solution was stirred for 10 minutes to evenly disperse the activated carbon in the solution. Then, this dispersion was allowed to stand. After allowing to stand for 8 hours or more, the activated carbon was withdrawn from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 3B. In the deodorizing material, the total carrying amount (parts by mass) of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the activated charcoal, and the total carrying amount of the sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( (Mass part) was measured in the same manner as in Example 1A.

<Comparative Example 4B>
Preparation of activated carbon
As an organic material, a mixture of 100 parts by mass of granular coal pitch having a softening point of 280 ° C. and 1.3 parts by mass of trisacetylacetonatoitorium was supplied to a melt extruder and melt-mixed at a melting temperature of 320 ° C. Pitch fibers were obtained by spinning at a discharge rate of 20 g / min. The obtained pitch fibers were subjected to infusibilization treatment by raising the temperature in air from room temperature to 354 ° C. at a rate of 1 to 30 ° C./min for 54 minutes to obtain an activated carbon precursor which is an infusible pitch fiber. The obtained activated carbon precursor was activated by continuously introducing a gas having an _H2O concentration of 100% by volume into an activation furnace and heat-treating at an atmospheric temperature of 900 ° C. for 25 minutes to obtain a fibrous activated carbon. .. The pore volume of the obtained fibrous activated carbon having a pore diameter of 0.65 nm or more and 2.0 nm or less was 0.337 cc / g. The total pore volume is 1.039 cc / g, the pore volume with a pore diameter of 2 nm or less is 0.395 cc / g, the specific surface area is 1248 m ² / g, and the pore volume with a pore diameter of 0.65 nm or less is 0. The pore volume with a pore diameter of 2 nm or more and 3 nm or less was 0.194 cc / g, and the pore volume with a pore diameter of 3 nm or more was 0.450 cc / g.

Supporting the chemical contained in the deodorant of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the chemical solution B prepared in Example 1B. Subsequently, the solution was stirred for 10 minutes to evenly disperse the activated carbon in the solution. Then, this dispersion was allowed to stand. After allowing to stand for 8 hours or more, the activated carbon was withdrawn from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 4B. In the deodorizing material, the total carrying amount (parts by mass) of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the activated charcoal, and the total carrying amount of the sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( (Mass part) was measured in the same manner as in Example 1A.

Using the deodorizing materials obtained in Examples 1B, 2B, and Comparative Examples 1B to 4B, the specific surface area and the acetaldehyde equilibrium adsorption amount were measured according to the above-mentioned method. Further, the specific surface area of the activated carbon was subtracted from the specific surface area of the obtained deodorant, and the specific surface area reduced by the support of aromatic amine and sulfuric acid was calculated. Further, the acetaldehyde equilibrium adsorption amount was evaluated by the ratio when the equilibrium adsorption amount of Comparative Example 2A was 1. The results are shown in Table 2.

<Summary of Test Example B>
In Examples 1B and 2B, the activated carbon and the sulfate of (A) aromatic amine and the aromatic amine supported on the activated carbon, or (B) the aromatic amine, the sulfate of the aromatic amine, and It is a deodorizing material containing sulfuric acid, and since the activated carbon has a pore volume of 0.65 nm or more and 2.0 nm or less and a pore volume of 0.6 cc / g or more, it can be used with aromatic amino acids under the same immersion conditions. Compared to the case where sulfuric acid is supported on activated carbon other than the above activated carbon, that is, activated carbon of Comparative Examples 1B to 4B having a pore diameter of 0.65 nm or more and 2.0 nm or less and a pore volume of less than 0.6 cc / g. Therefore, it exhibited excellent acetaldehyde adsorption performance.

[Test Example C]
<Example 1C>
Preparation of activated carbon
The activated carbon obtained in Example 1A was prepared.

Preparation of Chemical Solution C Contained in Deodorant of the Present Invention First, a sulfuric acid aqueous solution containing sulfuric acid at a concentration of 75% by mass was prepared. This sulfuric acid aqueous solution is stirred at a temperature of 65 ° C. or higher, p-aminobenzoic acid as an aromatic amine is added to the aqueous solution to completely dissolve it, and then the ratio of the mass of the activated charcoal to the volume of the treatment liquid is 20 g / L. Water was added so as to obtain a treatment liquid. The amount of aromatic amine and sulfuric acid charged was set to 30.0 parts by mass with respect to 100 parts by mass of activated carbon. The amount of sulfuric acid charged (parts by mass) indicates the amount (parts by mass) of sulfuric acid only excluding pure water in the 75 aqueous sulfuric acid solution.

Supporting the chemical contained in the deodorant of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the chemical solution C. Subsequently, the solution was stirred for 10 minutes to evenly disperse the activated carbon in the solution. Then, this dispersion was allowed to stand. After allowing to stand for 8 hours or more, the activated carbon was withdrawn from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Example 1C. In the deodorizing material, the total carrying amount (parts by mass) of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the activated charcoal, and the total carrying amount of the sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( (Mass part) was measured in the same manner as in Example 1A.

<Example 2C>
Preparation of activated carbon
The activated carbon obtained in Example 2B was prepared.

Supporting the chemical contained in the deodorant of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the chemical solution C prepared in Example 1C. Subsequently, the solution was stirred for 10 minutes to evenly disperse the activated carbon in the solution. Then, this dispersion was allowed to stand. After allowing to stand for 8 hours or more, the activated carbon was withdrawn from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Example 2C. In the deodorizing material, the total carrying amount (parts by mass) of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the activated charcoal, and the total carrying amount of the sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( (Mass part) was measured in the same manner as in Example 1A.

<Comparative Example 1C>
Preparation of activated carbon
The activated carbon obtained in Comparative Example 1A was prepared.

Supporting the chemical contained in the deodorant of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the chemical solution C prepared in Example 1C. Subsequently, the solution was stirred for 10 minutes to evenly disperse the activated carbon in the solution. Then, this dispersion was allowed to stand. After allowing to stand for 8 hours or more, the activated carbon was withdrawn from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 1B. In the deodorizing material, the total carrying amount (parts by mass) of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the activated charcoal, and the total carrying amount of the sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( (Mass part) was measured in the same manner as in Example 1A.

<Comparative Example 2C>
Preparation of activated carbon
The activated carbon obtained in Comparative Example 2A was prepared.

Supporting the chemical contained in the deodorant of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the chemical solution C prepared in Example 1C. Subsequently, the solution was stirred for 10 minutes to evenly disperse the activated carbon in the solution. Then, this dispersion was allowed to stand. After allowing to stand for 8 hours or more, the activated carbon was pulled out of the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 2C. In the deodorizing material, the total carrying amount (parts by mass) of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the activated charcoal, and the total carrying amount of the sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( (Mass part) was measured in the same manner as in Example 1A.

<Comparative Example 3C>
Preparation of activated carbon
The activated carbon obtained in Comparative Example 3A was prepared.

Supporting the chemical contained in the deodorant of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the chemical solution C prepared in Example 1C. Subsequently, the solution was stirred for 10 minutes to evenly disperse the activated carbon in the solution. Then, this dispersion was allowed to stand. After allowing to stand for 8 hours or more, the activated carbon was withdrawn from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 3C. In the deodorizing material, the total carrying amount (parts by mass) of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the activated charcoal, and the total carrying amount of the sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( (Mass part) was measured in the same manner as in Example 1A.

<Comparative Example 4C>
Preparation of activated carbon
The activated carbon obtained in Comparative Example 4B was prepared.

Supporting the chemical contained in the deodorant of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the chemical solution C prepared in Example 1C. Subsequently, the solution was stirred for 10 minutes to evenly disperse the activated carbon in the solution. Then, this dispersion was allowed to stand. After allowing to stand for 8 hours or more, the activated carbon was withdrawn from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 4C. In the deodorizing material, the total carrying amount (parts by mass) of the aromatic amine and the sulfate of the aromatic amine with respect to 100 parts by mass of the activated charcoal, and the total carrying amount of the sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( (Mass part) was measured in the same manner as in Example 1A.

Using the deodorizing materials obtained in Examples 1C, 2C, and Comparative Examples 1C to 4C, the specific surface area and the amount of acetaldehyde equilibrium adsorption were measured according to the above-mentioned method. Further, the specific surface area of the activated carbon was subtracted from the specific surface area of the obtained deodorant, and the specific surface area reduced by the support of aromatic amine and sulfuric acid was calculated. Further, the acetaldehyde equilibrium adsorption amount was evaluated by the ratio when the equilibrium adsorption amount of Comparative Example 2A was 1. The results are shown in Table 3.

<Summary of Test Example C>
In Examples 1C and 2C, activated carbon and (A) aromatic amine and sulfate of the aromatic amine supported on the activated carbon, or (B) aromatic amine, sulfate of the aromatic amine, and It is a deodorizing material containing sulfuric acid, and since the activated carbon has a pore volume of 0.65 nm or more and 2.0 nm or less and a pore volume of 0.6 cc / g or more, it can be used with aromatic amino acids under the same immersion conditions. Compared to the case where sulfuric acid is supported on activated carbon other than the above activated carbon, that is, activated carbon of Comparative Examples 1C to 4C having a pore diameter of 0.65 nm or more and 2.0 nm or less and a pore volume of less than 0.6 cc / g. Therefore, it exhibited excellent acetaldehyde adsorption performance.

Further, for Examples 1C and 2C in Test Example C, the pore distribution of the activated carbon before the drug was supported and the deodorizing material after the drug was supported was measured. The measured pore distribution is shown in Tables 4 and 5.

From Tables 4 and 5, it was clarified that the reduction rate of the pore volume in the range of 0.65 to 2.0 nm was high. This is considered to indicate that more of the above-mentioned drug is supported in the pores having a pore diameter in the range, among all the pore diameters.

[Test Example D]
(Example 1D (manufacturing of deodorizing sheet))
The deodorant obtained in Example 2B and the binder fiber (trade name Melty 4080 manufactured by Unitika Ltd.) are mixed so that the mass ratio (binder / deodorant) is 25/75, and a non-woven fabric web is used by a carding method. Was formed. A predetermined number of the obtained non-woven fabric webs are laminated, the fibers are entangled by needle punching, and then the binder fibers are melted by heating at a temperature of 110 ° C., and the binder fibers and the deodorizing material are fused to obtain a thickness of 0. A deodorizing sheet having a density of 65 mm and a density of 0.12 g / cm ³ was obtained. The basis weight of the deodorizing material in the deodorizing sheet was 56 g / m ² .

(Example 2D)
The deodorant obtained in Example 2C and the binder fiber (trade name Melty 4080 manufactured by Unitika Ltd.) are mixed so that the mass ratio (binder / deodorant) is 25/75, and a non-woven fabric web is used by a carding method. Was formed. A predetermined number of the obtained non-woven fabric webs are laminated, the fibers are entangled by needle punching, and then the binder fibers are melted by heating at a temperature of 110 ° C., and the binder fibers and the deodorizing material are fused to obtain a thickness of 0. A deodorizing sheet having a density of 65 mm and a density of 0.12 g / cm ³ was obtained. The basis weight of the deodorizing material in the deodorizing sheet was 56 g / m ² .

(Example 3D)
The deodorant obtained in Example 2C and the binder fiber (trade name Melty 4080 manufactured by Unitika Ltd.) are mixed so that the mass ratio (binder / deodorant) is 72/28, and a non-woven fabric web is used by a carding method. Was formed. A predetermined number of the obtained non-woven fabric webs are laminated, the fibers are entangled by needle punching, and then the binder fibers are melted by heating at a temperature of 110 ° C., and the binder fibers and the deodorizing material are fused to obtain a thickness of 0. A deodorizing sheet having a density of 35 mm and a density of 0.14 g / cm ³ was obtained. The basis weight of the deodorizing material in the deodorizing sheet was 14 g / m ² .

(Performance evaluation of deodorizing sheet)
A sample piece of an arbitrary weight of the obtained deodorizing sheet and 3 L of 100 ppm acetaldehyde gas were sealed in a closed container and allowed to stand in an environment of 40 ° C. After 24 hours, the gas concentration in the container was measured and the adsorption amount was calculated. Measurements were made for multiple sample weights, the correlation between the concentration and the adsorption amount was plotted on a graph from each calculation result, and the equilibrium adsorption amount (mg / g ACF) of acetaldehyde at an arbitrary equilibrium concentration was calculated from the obtained relational expression. lead. The concentration of acetaldehyde was measured by gas chromatography.

The results of Examples 1D to 3D are shown in Table 6.

As shown in Table 6, since the deodorizing sheets of Examples 1D to 3D contain the deodorizing material of the present invention, the acetaldehyde adsorption performance was efficiently exhibited.

Claims (8)

A deodorant containing the activated charcoal and (A) aromatic amine and sulfate of the aromatic amine supported on the activated charcoal, or (B) aromatic amine, sulfate of the aromatic amine, and sulfuric acid. And
The activated carbon before supporting the (A) or the (B) is an acetaldehyde or formaldehyde deodorant having a pore volume of 0.65 nm or more and 2.0 nm or less and a pore volume of 0.6 cc / g or more. The activated carbon before supporting the (A) or the (B) has a total pore volume (cc / g) of 1 to 2 times the pore volume having a pore diameter of 0.65 nm or more and 2.0 nm or less. , The deodorizing material of claim 1. The deodorant according to claim 1 or 2, wherein the activated carbon before supporting the (A) or the (B) has a pore volume of 3 nm or more and a pore volume of 0.02 cc / g or less. The deodorant according to any one of claims 1 to 3, wherein the specific surface area of the activated carbon before supporting the (A) or the (B) is 1500 m ² / g or more. The deodorant according to any one of claims 1 to 4, wherein the specific surface area of the deodorant is 400 to 1200 m ² / g. The value obtained by subtracting the specific surface area of the deodorizing material from the specific surface area of the activated carbon before supporting the (A) or the (B) is 800 to 1300 m ² / g, according to any one of claims 1 to 5. The deodorant material described. The deodorant according to any one of claims 1 to 6, wherein the equilibrium adsorption amount (mg / gACF) of acetaldehyde at an equilibrium concentration of 10 ppm is 35 mg / gACF or more. A deodorizing sheet for acetaldehyde or formaldehyde containing the deodorizing material according to any one of claims 1 to 7.